EP3142179B1 - Procédé de fabrication d'une membrane d'électrolyte inorganique ayant une compacité améliorée, composition pour la fabrication de membrane d'électrolyte inorganique, et membrane d'électrolyte inorganique fabriquée utilisant ceux-ci - Google Patents
Procédé de fabrication d'une membrane d'électrolyte inorganique ayant une compacité améliorée, composition pour la fabrication de membrane d'électrolyte inorganique, et membrane d'électrolyte inorganique fabriquée utilisant ceux-ci Download PDFInfo
- Publication number
- EP3142179B1 EP3142179B1 EP15827823.4A EP15827823A EP3142179B1 EP 3142179 B1 EP3142179 B1 EP 3142179B1 EP 15827823 A EP15827823 A EP 15827823A EP 3142179 B1 EP3142179 B1 EP 3142179B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- inorganic particles
- electrolyte membrane
- dispersant
- green sheet
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000012528 membrane Substances 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 title claims description 12
- 239000010954 inorganic particle Substances 0.000 claims description 78
- 239000002270 dispersing agent Substances 0.000 claims description 48
- 239000006185 dispersion Substances 0.000 claims description 43
- 239000011230 binding agent Substances 0.000 claims description 37
- 238000002296 dynamic light scattering Methods 0.000 claims description 26
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 14
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- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000003746 surface roughness Effects 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 20
- 238000000576 coating method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 13
- 239000002002 slurry Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000000446 fuel Substances 0.000 description 12
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- 238000005259 measurement Methods 0.000 description 10
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 8
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 7
- 239000011324 bead Substances 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PACGUUNWTMTWCF-UHFFFAOYSA-N [Sr].[La] Chemical compound [Sr].[La] PACGUUNWTMTWCF-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000010296 bead milling Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- LFKMKZZIPDISEK-UHFFFAOYSA-L magnesium;4-carboxy-2,6-dihydroxyphenolate Chemical compound [Mg+2].OC1=CC(C([O-])=O)=CC(O)=C1O.OC1=CC(C([O-])=O)=CC(O)=C1O LFKMKZZIPDISEK-UHFFFAOYSA-L 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- QBYHSJRFOXINMH-UHFFFAOYSA-N [Co].[Sr].[La] Chemical compound [Co].[Sr].[La] QBYHSJRFOXINMH-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
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- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
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- 239000007784 solid electrolyte Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
- H01M2300/0074—Ion conductive at high temperature
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a method of manufacturing an inorganic electrolyte membrane having improved compactness, a composition for manufacturing an inorganic electrolyte membrane, and an inorganic electrolyte membrane manufactured using the same.
- an inorganic thin film having high compactness may be formed in a manner in which inorganic particles are dispersed in a binder and a solvent and the resulting solution is applied using any coating process to form a thin film, which is then fired at a high temperature to remove the binder.
- the compactness of the inorganic thin film is determined based on the extent of dispersion of inorganic particles and the amount of binder.
- the firing temperature may be adjusted depending on the size of the primary inorganic particles. For example, the use of nano-sized inorganic particles enables the firing temperature to be lowered.
- This method may be utilized in the field of a solid oxide fuel cell (SOFC).
- SOFC solid oxide fuel cell
- a fuel cell is a device for directly converting the chemical energy of fuel into electrical energy through an electrochemical reaction, and is advantageous because it has high energy conversion efficiency compared to typical heat engines, thus reducing fuel consumption and greenhouse gas emissions.
- a fuel cell especially a solid oxide fuel cell, uses an inorganic electrolyte membrane having high ion conductivity at high temperatures.
- an inorganic electrolyte for an SOFC has high ion conductivity at high operating temperatures (800 to 1,000°C), thus making it difficult to manufacture and maintain a fuel cell stack.
- JP2009104990 discloses a method of manufacturing an inorganic electrolyte membraneaccording to the preamble of claim 1.
- the present invention is intended to provide a method of manufacturing an inorganic electrolyte membrane having high compactness and high ion conductivity in order to develop a solid oxide fuel cell (SOFC) that may operate at high efficiency at intermediate temperatures of 650 to 700°C.
- SOFC solid oxide fuel cell
- the present invention provides a method of manufacturing an inorganic electrolyte membrane, comprising: (a) mixing primary inorganic particles ( ⁇ 50 nm), a dispersant, and a solvent and dispersing the primary inorganic particles, thus preparing a dispersion of secondary inorganic particles having a hydrodynamic diameter of 120 to 230 nm, determined using DLS (Dynamic Light Scattering); (b) adding and mixing the dispersion of secondary inorganic particles with a binder; (c) applying a mixed solution comprising the dispersion of secondary inorganic particles and the binder and drying the mixed solution, thus forming a green sheet; and (d) firing the green sheet, thus forming an electrolyte membrane.
- DLS Dynamic Light Scattering
- the present invention provides a composition for manufacturing an inorganic electrolyte membrane, comprising a binder and a dispersion of secondary inorganic particles, having a hydrodynamic diameter of 120 to 230 nm determined using DLS (Dynamic Light Scattering), by dispersing primary inorganic particles ( ⁇ 50 nm).
- a composition for manufacturing an inorganic electrolyte membrane comprising a binder and a dispersion of secondary inorganic particles, having a hydrodynamic diameter of 120 to 230 nm determined using DLS (Dynamic Light Scattering), by dispersing primary inorganic particles ( ⁇ 50 nm).
- the present invention provides a green sheet, manufactured by applying and drying the composition for manufacturing an inorganic electrolyte membrane.
- the present invention provides an inorganic electrolyte membrane, manufactured by firing the green sheet.
- the present invention provides a solid oxide fuel cell, including the inorganic electrolyte membrane.
- a method of manufacturing an inorganic electrolyte membrane reduces the amount of energy necessary for dispersing inorganic particles, and enables the formation of an inorganic electrolyte membrane layer having high compactness and high density, thereby preventing electrical conduction between an air layer and a fuel layer and also suppressing non-uniformity and cracking, consequently increasing reproducibility upon cell fabrication.
- the present invention addresses a method of manufacturing an inorganic electrolyte membrane, comprising: (a) mixing primary inorganic particles ( ⁇ 50 nm), a dispersant, and a solvent and dispersing the primary inorganic particles, thus preparing a dispersion of secondary inorganic particles having a hydrodynamic diameter of 120 to 230 nm, determined using DLS (Dynamic Light Scattering); (b) adding and mixing the dispersion of secondary inorganic particles with a binder; (c) applying a mixed solution comprising the dispersion of secondary inorganic particles and the binder and drying it, thus forming a green sheet; and (d) firing the green sheet, thereby forming an electrolyte membrane.
- DLS Dynamic Light Scattering
- an inorganic electrolyte membrane layer having high compactness and high density may be formed, in which non-uniformity and cracking may be prevented.
- compactness refers to the ratio (porosity of 2% or less) of a substantial structure in an inorganic membrane, and may be determined through a variety of methods. For example, it may be measured using an Archimedes density measurement method, but the present invention is not necessarily limited thereto.
- the present invention includes (a) mixing primary inorganic particles ( ⁇ 50 nm), a dispersant, and a solvent, and then dispersing the primary inorganic particles, thus preparing a dispersion of secondary inorganic particles having a hydrodynamic diameter of 120 to 230 nm, determined using DLS (Dynamic Light Scattering).
- the dispersant may be a cationic dispersant, and is preferably an acrylate copolymer dispersant or a polyurethane-based dispersant.
- the dispersant may be contained in an amount of 9 parts by weight, or 12 or 15 parts by weight, based on 100 parts by weight of the inorganic particles in terms of SOP (Solids On Pigment).
- the amount of the dispersant is 10 to 20 parts by weight based on 100 parts by weight of the inorganic particles, but the present invention is not necessarily limited thereto.
- the amount of the dispersant is less than 10 parts by weight based on 100 parts by weight of the inorganic particles, a dispersant layer thinner than 10 nm may be formed on the surface of the secondary inorganic particles, making it difficult to substantially disperse such particles.
- the amount thereof exceeds 20 parts by weight, a negative effect on the sintering process due to stress may occur.
- the primary inorganic particles may be any one or more selected from the group consisting of GDC (Gadolinium-Doped Ceria), LDC (Lanthanum-Doped Ceria), LSGM (Lanthanum Strontium Gallium Magnesium oxide, or strontium and magnesium-doped lanthanum gallate), YSZ (Yttrium-Stabilized Zirconia) and ScSZr (Sc-Stabilized Zirconia).
- GDC Gadolinium-Doped Ceria
- the GDC may take the form of a secondary structure, and the primary inorganic particles, which are first fed before the dispersing process, may have a particle size of 50 nm or less, as measured using a microscope such as a TEM or SEM.
- the solvent may be any one or more selected from the group consisting of alcohol, PGME (Propylene Glycol Methyl Ether), PGMEA (Propylene Glycol Methyl Ethyl Acetate), MEK (Methyl Ethyl Ketone), MIBK (Methyl IsoButyl Ketone), toluene, terpineol, DMF and DMSO.
- the solvent may be contained in an amount of 50 to 90 parts by weight based on 100 parts by weight of the inorganic particles.
- the primary inorganic particles ( ⁇ 50 nm), the dispersant and the solvent are mixed and then dispersed, thus preparing a dispersion of secondary inorganic particles having a hydrodynamic diameter of 120 to 230 nm, determined using DLS (Dynamic Light Scattering).
- DLS Dynamic Light Scattering
- hydrodynamic diameter may be defined as the diameter obtained by calculating the ratio of a circumference wet by a fluid in a pipe having a cross-section of any shape other than a circular shape to the actual area of the pipe, on the basis of a circle, and may be measured using dynamic light scattering (DLS).
- DLS dynamic light scattering
- the dispersing process may be performed through a shear force-induced dispersing process, such as high-pressure homogenization, bead milling, bead shaking, ball milling or the like.
- a shear force-induced dispersing process such as high-pressure homogenization, bead milling, bead shaking, ball milling or the like.
- Preferably useful is bead shaking.
- the hydrodynamic diameter of the secondary inorganic particles in the dispersion may range from 120 to 230 nm, preferably 150 to 230 nm, and more preferably 180 to 230 nm.
- the present invention includes (b) adding and mixing the dispersion of secondary inorganic particles with a binder.
- the binder is used to bind inorganic particles, and is responsible for maintaining the form of a sheet and ensuring processability for forming a membrane. Like the solvent, the binder is used in as small an amount as possible to impart adhesion so as to ensure desired processability.
- the binder may include a polymer that may be removed at 500°C or lower, such as an acrylate-based binder, a urethane-based binder, and a cellulose-based binder. Preferably useful is an acrylate-based compound.
- the binder may be contained in an amount of 2.5 to 5 parts by weight based on 100 parts by weight of the dispersion of secondary inorganic particles, but the present invention is not limited thereto.
- a plasticizer may be further added as necessary.
- the plasticizer is not particularly limited so long as it is typically useful in the art.
- the mixing of b) may be performed through a shear force-induced dispersing process, such as high-pressure homogenization, bead milling, bead shaking, ball milling or the like.
- a shear force-induced dispersing process such as high-pressure homogenization, bead milling, bead shaking, ball milling or the like.
- Preferably useful is bead shaking.
- the present invention includes (c) manufacturing a green sheet by applying a mixed solution comprising the dispersion of inorganic particles and the binder and then drying it.
- the mixed solution comprising the dispersion and the binder may be applied using a coating process such as comma coating, blade coating, DIE coating, or LIP coating.
- a coating process such as comma coating, blade coating, DIE coating, or LIP coating.
- the green sheet is formed through comma coating. After the coating process, drying is preferably performed for 10 min or more.
- the dried green sheet may have a surface roughness Ra, that is, a center line average roughness, of 0.8 ⁇ m or less.
- the dried green sheet may have a gloss of 10 GU (60°) or more, or 20 GU (85°) or more.
- the present invention includes (d) firing the green sheet to form an electrolyte membrane.
- the firing is preferably carried out at 1300 to 1600°C for 1 hr or more.
- the present invention addresses a composition for manufacturing an inorganic electrolyte membrane, comprising a binder and a dispersion of secondary inorganic particles having a hydrodynamic diameter of 120 to 230 nm determined using DLS (Dynamic Light Scattering), by dispersing primary inorganic particles ( ⁇ 50 nm).
- a composition for manufacturing an inorganic electrolyte membrane comprising a binder and a dispersion of secondary inorganic particles having a hydrodynamic diameter of 120 to 230 nm determined using DLS (Dynamic Light Scattering), by dispersing primary inorganic particles ( ⁇ 50 nm).
- the dispersant may be a cationic dispersant, and preferably an acrylate copolymer dispersant or a polyurethane-based dispersant.
- the dispersant may be contained in an amount of 9 parts by weight, or 12 or 15 parts by weight, based on 100 parts by weight of the inorganic particles in terms of SOP (Solids On Pigment).
- the amount of the dispersant is 10 to 20 parts by weight based on 100 parts by weight of the inorganic particles, but the present invention is not necessarily limited thereto.
- the amount of the dispersant is less than 10 parts by weight based on 100 parts by weight of the inorganic particles, a dispersant layer thinner than 10 nm may be formed on the surface of the secondary inorganic particles, making it difficult to substantially disperse such particles.
- the amount thereof exceeds 20 parts by weight, a negative effect on the sintering process due to stress may occur.
- the primary inorganic particles may be any one or more selected from the group consisting of GDC (Gadolinium-Doped Ceria), LDC (Lanthanum-Doped Ceria), LSGM (Lanthanum Strontium Gallium Magnesium oxide, or strontium and magnesium-doped lanthanum gallate), YSZ (Yttrium-Stabilized Zirconia) and ScSZr (Sc-Stabilized Zirconia).
- GDC Gadolinium-Doped Ceria
- the GDC may take the form of a secondary structure, and the primary inorganic particles, which are first fed before the dispersing process, may have a particle size of 50 nm or less, as measured using a microscope such as a TEM or SEM.
- the solvent may be any one or more selected from the group consisting of alcohol, PGME (Propylene Glycol Methyl Ether), PGMEA (Propylene Glycol Methyl Ethyl Acetate), MEK (Methyl Ethyl Ketone), MIBK (Methyl IsoButyl Ketone), toluene, terpineol, DMF and DMSO.
- the solvent may be contained in an amount of 50 to 90 parts by weight based on 100 parts by weight of the inorganic particles.
- the binder is used to bind inorganic particles, and is responsible for maintaining the form of a sheet and ensuring processability for forming a membrane. Like the solvent, the binder is used in as small an amount as possible to impart adhesion so as to ensure desired processability.
- the binder may include a polymer that may be removed at 500°C or lower, such as an acrylate-based binder, a urethane-based binder, and a cellulose-based binder. An acrylate-based compound is preferably used.
- the binder may be contained in an amount of 2.5 to 5 parts by weight based on 100 parts by weight of the dispersion of secondary inorganic particles, but the present invention is not limited thereto.
- the green sheet may be formed through a coating process using the composition for manufacturing an inorganic electrolyte membrane, and the coating process may include comma coating, blade coating, DIE coating, or LIP coating. Preferably useful is comma coating. After the coating process, drying may be performed for 10 min or longer.
- the dried green sheet may have a surface roughness Ra, that is, a center line average roughness, of 0.8 ⁇ m or less.
- the dried green sheet may have a gloss of 10 GU (60°) or more, or 20 GU (85°) or more.
- the present invention addresses a solid oxide fuel cell including the inorganic electrolyte membrane.
- a 30 ml vial 6.4 g of, as primary inorganic particles, GDC powder (made by Rhodia, UHSA grade, primary particle size: ⁇ 30 nm) and 2.1 g (20 in terms of SOP) of a dispersant (BYK-112, solid content: 60%), corresponding to 20 parts by weight based on 100 parts by weight of the inorganic particles, were mixed with 4.2 g of toluene, after which balls (3 mm ZrO 2 ) were placed in the vial, and a dispersing process was then performed for 24 hr and 72 hr.
- GDC powder made by Rhodia, UHSA grade, primary particle size: ⁇ 30 nm
- a dispersant BYK-112, solid content: 60%
- a binder made by SOKEN, LRRS001
- a plasticizer made by Aldrich, dibutylphthalate (DBP)
- a slurry was prepared in the same manner as in Example 1, with the exception that 1.2 g (SOP 10) of a dispersant (BYK-112, solid content: 60%), corresponding to 10 parts by weight based on 100 parts by weight of the inorganic particles, and 4.9 g of toluene were used.
- a slurry was prepared in the same manner as in Example 1, with the exception that 2.8 g (SOP 20) of a dispersant (BYK-163, solid content: 45%), corresponding to 20 parts by weight based on 100 parts by weight of the inorganic particles, and 3.5 g of toluene were used.
- a slurry was prepared in the same manner as in Example 1, with the exception that 1.4 g (SOP 10) of a dispersant (BYK-163, solid content: 45%), corresponding to 10 parts by weight based on 100 parts by weight of the inorganic particles, and 4.9 g of toluene were used.
- a 30 ml vial 6.4 g of, as primary inorganic particles, GDC powder (made by Rhodia, UHSA grade, primary particle size: ⁇ 30 nm) and 0.55 g (SOP 5) of a dispersant (BYK-112, solid content: 60%), corresponding to 5 parts by weight based on 100 parts by weight of the inorganic particles, were mixed with 5.75 g of toluene, balls (3 mm ZrO 2 ) were placed in the vial, and a dispersing process was performed for 24 hr and 72 hr. The dispersibility of the resulting slurry was determined through particle size measurement using DLS.
- a binder made by SOKEN, LRRS001
- a plasticizer made by Aldrich, dibutylphthalate (DBP)
- a binder made by SOKEN, LRRS001
- a plasticizer made by Aldrich, dibutylphthalate (DBP)
- a binder made by SOKEN, LRRS001
- a plasticizer made by Aldrich, dibutylphthalate (DBP)
- a binder made by SOKEN, LRRS001
- a plasticizer made by Aldrich, dibutylphthalate (DBP)
- a 30 ml vial 6.4 g of, as primary inorganic particles, GDC powder (made by Rhodia, UHSA grade, primary particle size: ⁇ 30 nm) and 1.28 g (SOP 20) of a dispersant (BYK-111, anionic dispersant, solid content: 95%), corresponding to 10 parts by weight based on 100 parts by weight of the inorganic particles, were mixed with 5.75 g of toluene, balls (3 mm ZrO 2 ) were placed in the vial, and a dispersing process was performed for 24 hr and 72 hr. The dispersibility of the resulting slurry was determined through particle size measurement using DLS.
- the size (hydrodynamic diameter) of secondary particles of the dispersions of the above Comparative Examples and Examples was measured using DLS (Dynamic Light Scattering) before the addition of the binder and the plasticizer.
- DLS Dynamic Light Scattering
- the particle size was measured from the dispersion of each Example. The results are shown in Table 1.
- the particle size was decreased with an increase in the amount of the dispersant in the dispersion of each Example.
- the particle size of GDC was decreased due to steric stabilization based on the dispersant, and dispersibility was increased.
- Comparative Examples 1 to 3 containing the dispersant in too small an amount, and Comparative Example 5, using an anionic dispersant, dispersibility was poor and the particle size of GDC was excessively increased.
- a dispersion in which the size of the secondary particles was 210 nm or less was prepared depending on the dispersing process in Comparative Example 4 of Table 1. In this case, however, dispersibility was excessively increased and it became possible to apply high stress to a cell upon firing, undesirably deteriorating stability and breaking the cell.
- Test Example 2 Measurement of gloss of dispersion through PET film coating
- Test Example 3 Measurement of optical profile of dispersion through PET film coating
- the resulting coating film was measured using an optical profile meter.
- the surface roughness was decreased due to the addition of the dispersant to the dispersion of each Example. Accordingly, the particle size of GDC was decreased due to steric stabilization based on the dispersant, and dispersibility was increased.
- Test Example 4 Measurement of compactness of electrolyte membrane through sintering
- the electrolyte layers of Examples 1 and 3 were found to have high compactness and a large domain size, as shown in the surface images of FIG. 1 .
- the electrolyte layer of Comparative Example 2 was observed to be non-uniform and cracked due to the decreased dispersibility of the particles, as shown in FIG. 2 .
- the sample of Comparative Example 3 was observed to have low uniformity and to be cracked after firing at a low temperature (1400°C), as shown in FIG. 3 . This was the same as the sample of FIG. 2 .
- the sample of Comparative Example 4 exhibited high dispersibility using a bead mill, but high stress was applied to the cell due to excessively high dispersibility after firing, undesirably breaking the cell.
- Test Example 5 Measurement of cell performance using electrolyte membrane
- the cell was manufactured using a cathode (a lanthanum strontium cobalt ferrite (LSCF) cathode, LG chem.), an anode [(NiO, ⁇ 200 nm, made by J.T. Baker), carbon black (N990, made by Columbian), GDC (ULSA, made by Rhodia)], and the electrolyte membrane of Test Example 4.
- LSCF lanthanum strontium cobalt ferrite
- the electrolyte membrane of Test Example 4 was layered on the NiO anode and then sintered at 1500°C, after which the LSCF cathode was layered thereon and then sintered at 1000°C, thus completing a cell.
Claims (11)
- Procédé de fabrication d'une membrane électrolytique inorganique, le procédé comprenant :a) le mélange de particules inorganiques primaires, d'un dispersant et d'un solvant et la dispersion des particules inorganiques primaires, en préparant ainsi une dispersion de particules inorganiques secondaires ayant un diamètre hydrodynamique de 120 à 230 nm, déterminé par diffusion dynamique de lumière (DLS) ;b) l'ajout et le mélange d'un liant à la dispersion de particules inorganiques secondaires ;c) l'application d'une solution mixte comprenant la dispersion de particules inorganiques secondaires et le liant et le séchage de la solution mixte, en formant ainsi une feuille crue ; etd) la cuisson de la feuille crue, en formant ainsi une membrane électrolytique,dans lequel les particules inorganiques primaires présentent, avant leur dispersion, un diamètre de particule inférieur à 50 nm, mesuré à l'aide d'un MET ou d'un MEB,
caractérisé en ce que
le dispersant est un dispersant de type copolymère d'acrylate ou un dispersant à base de polyuréthane, et
en ce que
le dispersant est présent en une quantité de 10 à 20 parties en poids rapportée à 100 parties en poids des particules inorganiques primaires en termes de matières solides sur pigment (SOP). - Procédé selon la revendication 1, dans lequel les particules inorganiques primaires sont en GDC (cérine dopée au gadolinium).
- Procédé selon la revendication 1, dans lequel la feuille crue obtenue à (c) présente une rugosité de surface Ra inférieure ou égale à 0,8 µm.
- Procédé selon la revendication 1, dans lequel la feuille crue obtenue à (c) présente un brillant supérieur ou égal à 10 GU (60°).
- Composition pour la fabrication d'une membrane électrolytique inorganique, la composition comprenant un liant et une dispersion de particules inorganiques secondaires ayant un diamètre hydrodynamique de 120 à 230 nm déterminé par diffusion dynamique de lumière (DLS), résultant de la dispersion de particules inorganiques primaires,
dans laquelle les particules inorganiques primaires présentent, avant la dispersion, un diamètre de particule inférieur à 50 nm, mesuré à l'aide d'un MET ou d'un MEB,
dans laquelle la dispersion comprend un dispersant et un solvant,
caractérisée en ce que
le dispersant est un dispersant de type copolymère d'acrylate ou un dispersant à base de polyuréthane, et
en ce que
le dispersant est présent en une quantité de 10 à 20 parties en poids rapportée à 100 parties en poids des particules inorganiques primaires en termes de matières solides sur pigment (SOP). - Composition selon la revendication 5, dans laquelle les particules inorganiques primaires sont en GDC (cérine dopée au gadolinium).
- Composition selon la revendication 5, dans laquelle le solvant est présent en une quantité de 80 à 90 parties en poids rapportée à 100 parties en poids des particules inorganiques primaires.
- Feuille crue, fabriquée par application et séchage de la composition selon la revendication 5.
- Feuille crue selon la revendication 8, dans laquelle la feuille crue présente une rugosité de surface Ra inférieure ou égale à 0,8 µm.
- Feuille crue selon la revendication 8, dans laquelle la feuille crue présente un brillant supérieur ou égal à 10 GU (60°).
- Membrane électrolytique inorganique fabriquée par cuisson de la feuille crue selon la revendication 8.
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